Synthesis and characterization of poly(methyl methacrylate)-block-poly(methylphenylsilane)-block-poly(methyl methacrylate) by atom transfer radical polymerization

ABA block copolymers of methyl methacrylate and methylpherylsilane were synthesized with a methodology based on atom transfer radical polymerization (ATRP). The reaction of samples of alpha,omega-dihalopoly(methylphenylsilane) with 2-hydroxyethyl-2-methyl-2-bromoproprionate gave suitable macroinitiators for the ATRP of methyl methacrylate. The latter procedure was carried out at 95 degreesC in a xylene solution with CuBr and 2,2-bipyridine as the initiating system. The rate of the polymerization was first-order with respect to monomer conversion. The block copolymers were characterized with H-1 NMR and C-13 NMR spectroscopy and size exclusion chromatography, and differential scanning calorimetry was used to obtain preliminary evidence of phase separation in the copolymer products. (C) 2002 Wiley Periodicals, Inc.